JP3217360B2 - Antifoaming agent in granular form - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a foam control agent in granular form, a method for producing such a foam control agent, and a detergent composition containing such a foam control agent.

BACKGROUND OF THE INVENTION It has become a common practice in the detergent industry to incorporate into a detergent composition a substance that seeks to control the amount of foam generated during the washing cycle in a washing machine.

In fact, excessive foaming has been found to interfere with the action of the cleaning liquid on the fabric.

Silicone antifoams have been found to be particularly effective, and numerous efforts have been made to increase the stability of such antifoams during prolonged storage of detergent compositions containing them. Has been turned.

GB 1,492,339 discloses that silicone antifoams can be prepared by reacting water-soluble or water-dispersible, substantially non-surfactant, detergent-impermeable substances such as gelatin, agar or tallow alcohol with ethylene oxide. Coating with the product organic material has been proposed.

EP-A 210 721 proposes coating a silicone antifoam with a water-insoluble fatty acid or fatty alcohol, and EP-A 210 731 discloses a silicone defoamer. Coating with a monoester of glycerol and a fatty acid is disclosed.

Such antifoams in particulate form, when incorporated into a detergent composition, appear to exhibit desirable stability upon storage,
It has been found that such defoamed granules are not ideally suited for easy incorporation into detergent compositions in powder form, such as dry blending.

Thus, it is an object of the present invention to provide a storage-stable foam control agent in the form of granules which is free flowing and can be easily processed into detergent compositions.

DISCLOSURE OF THE INVENTION The present invention is a stable, free-flowing, defoamer in granular form for incorporation into a powdered detergent composition comprising a silicone antifoam compound, a carrier material, preferably starch, an organic coating material, Stable free-flow control in granular form characterized by containing a crystalline or amorphous aluminosilicate in a weight ratio with the silicone antifoam compound of 1: 5 to 2: 1, preferably 1: 3 to 1: 1 Provide foaming agent.

The present invention also provides a method for producing such an antifoaming agent, and a detergent composition containing a surfactant, the antifoaming agent and optionally other detergent components.

BEST MODE FOR CARRYING OUT THE INVENTION Silicone Antifoam Compound The silicone antifoam compound is present in the foam control agent of the present invention in an amount of 5 to 20% by weight, preferably 8 to 15% by weight.

In industrial practice, the term "silicone" has become a general term encompassing various relatively high molecular weight polymers containing siloxane units and various hydrocarbyl groups. Generally, silicone foam control agents have a general structure Wherein each R can independently be an alkyl or aryl group. Examples of such substituents are methyl, ethyl, propyl, isobutyl, and phenyl. Preferred polydiorganosiloxanes have trimethylsilyl end blocking units and
Viscosity at 25 ° C. 5 × 10 ⁻⁵ m ² / s to 0.1 m ² / s, ie 40 to 150
Polydimethylsiloxane having a value of n in the range of 0. These are preferred because of their ready availability and relatively low cost.

A preferred type of silicone defoamer useful in the present compositions comprises a mixture of an alkylated siloxane of the type described above and solid silica.

Solid silica is fumed silica,
It can be precipitated silica or silica produced by gel-forming techniques. The silica particles suitably have an average particle size of 0.1 to 50 μm, preferably 1 to 20 μm and a surface area of at least 50 m ² / g. These silica particles are
Hydrophobicity can be achieved by treatment with dialkylsilyl and / or trialkylsilyl groups, either bonded directly on silica or bonded by a silicone resin. Preference is given to using silica, whose particles have been rendered hydrophobic with dimethyl and / or trimethylsilyl groups. The silicone defoamer used in the foam control agent according to the present invention is preferably 1 to 30% by weight of the total weight of the silicone defoamer (more preferably 2.0 to 1%).
5 have the amount of silica in the range of weight%), resulting in average viscosity 2 × 10 ^-4 m ² / s ~1m silicone antifoam having a ² / sec. Preferred silicone defoamers have a viscosity of 5 × 10 ⁻³ m ²
Per ^{second to} 0.1 m ² / sec. Silicone defoamers having a viscosity of 2 × 10 ^-2 m ² / s or 4.5 × 10 ^-2 m ² / s are particularly preferred.

Carrier material A carrier material for use herein provides a solid basis,
On top of this, a silicone antifoam and an organic coating substance adhere during manufacture. Therefore, the carrier material is compatible with the detergent components, is water soluble or water dispersible to facilitate dispersion of the silicone antifoam into the aqueous liquid during the wash cycle, and absorbs or absorbs the silicone antifoam. It must be in the form of solid particles that can be adsorbed.

The carrier material is present in the foam control agent in an amount of 50-90% by weight, preferably 60-90%.
It is present in an amount of 7575% by weight.

Preferred carrier materials for use in the foam control agents according to the invention are natural starches or starches which have been chemically modified by both hot or cold gelling in water. Other suitable materials are diatomaceous and fuller's earth.

Also, among the components that play an active role in the washing or washing method, it is possible to select the carrier particles to be used here. Examples of such materials are zeolites, sodium tripolyphosphate (STPP) particles, sodium sulfate,
Sodium citrate, sodium carbonate, carboxymethyl cellulose and clay minerals.

Organic Coating Material The organic coating material is one of the antifoaming agents according to the present invention.
It is present in an amount of 30% by weight, preferably 8-22% by weight.

Organic coating materials suitable for use in the granules of the present invention can be water-soluble / dispersible species, water-insoluble species, or mixtures thereof.

The water-soluble or water-dispersible carrier material must be impermeable to the detergent and must be substantially non-surfactant. Substantially non-surfactant means that the carrier material itself does not interact with the silicone material in such a way as to emulsify or otherwise overdisperse throughout the aqueous medium rather than at the air / water interface.

Various carrier materials having the requisite solubility / dispersion properties and the essential characteristics of being non-surfactant and detergent-impermeable are known. For example, high molecular weight carbowax having substantially no surfactant properties (Carbowax)
("Carbowax" is a trademark) is useful herein. Examples of this type of material include molecular weights of about 1,500 to about 1
Polyethylene glycols having a molecular weight of 0,000, especially about 4,000. Highly ethoxylated fatty alcohols,
For example, tallow alcohol condensed with about 25 mole fraction of ethylene oxide is useful herein. Other alcohol condensates containing very high ethoxylate ratios (about 80) are also useful herein.

Such high ethoxylates clearly lack sufficient surfactant properties to interact with or otherwise interfere with the desired foam control properties of the silicone agents herein. Particularly preferred ethoxylated carrier materials here are tallow alcohols, abbreviated TAE, condensed with about 80 mole proportions of ethylene oxide.
₈₀ .

Various other materials useful herein as water-soluble / dispersible coatings are also included, such as gelatin, agar, acacia, and various algae-derived gels.

Water-insoluble organic substances suitable for use in the foam control agents according to the present invention are water-insoluble fatty acids, fatty alcohols, fatty acid esters and mixtures thereof. Fatty acids or fatty alcohols are those with 10 to 20 carbons in the alkyl chain.

Suitable fatty acids are saturated or unsaturated and natural sources such as vegetable or animal esters such as palm oil, coconut oil, babassu oil, safflower oil, tall oil, castor oil, tallow and fish oil, grease, and Mixtures thereof) or can be prepared synthetically, for example, by oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process. Examples of fatty acids suitable for use in the present invention include capric, lauric, myristic, palmitic, stearic, arachiic, and behenic acids.

Stearic acid is preferred. Tallow (C ₁₆ ~C ₁₈₎ fatty acids, preferably. Alcohol derived from the fatty acid, wherein a suitable suds control agent, stearic alcohol and tallow (C ₁₆ ~C ₁₈₎ alcohols are preferred.

Esters of the fatty acids with _C1-3 alcohols, such as ethyl myristate, ethyl stearate, methyl palmitate, and glycerol monostearate are also suitable, the latter being particularly preferred.

Of the water-insoluble fatty substances, stearyl acid and stearyl alcohol are particularly preferred. These substances are
Preferred for good performance, easy availability and suitable melting point. The melting points of stearic acid and stearyl alcohol are 71.5 and 59.4 ° C., respectively, at which temperature they are insoluble in water. These materials do not appear to interfere with the effectiveness of the silicone antifoam when released into the cleaning fluid.

Mixtures of the water-soluble / dispersible coatings with the water-insoluble organic substances of the present invention are also suitable. A preferred mixture is stearyl alcohol and TAE ₈₀ .

The amount of organic coating material used in the antifoam of the present invention should be at least 1 part organic coating material per part silicone antifoam. It is preferred to use a weight ratio of organic coating material and silicone antifoam in the range of 5: 1 to 1: 2, more preferably 4: 1 to 1: 1.

The crystalline or amorphous aluminosilicate The aluminosilicate builder present in the composition of the present invention may be crystalline or amorphous or a mixture thereof, and has a general formula of 0.8 to 1.5 Na ₂ O.Al ₂ O ₃ - having 0.8~6SiO _2.

These materials are required to contain some bound water and have a calcium ion exchange capacity of at least about 50 mg CaO / g. Preferred aluminosilicates are 1.
It contains 5 to 3.5 SiO ₂ units (in the above formula) and has a particle size of about 10
It has 0μ or less, preferably about 20μ or less. Both amorphous and crystalline aluminosilicates can be readily formed by the reaction between sodium silicate and sodium aluminate as detailed in the literature.

Crystalline aluminosilicates (zeolites) are preferred for use in the present invention. Suitable materials are described, for example, in GB 1 429 143. Preferred sodium aluminosilicates of this type are the well-known commercial zeolites A and X, and mixtures thereof.
Zeolite type 4A is particularly preferred for use in the present invention.

Aluminosilicate is a weight ratio of the antifoaming agent of the present invention to the silicone antifoam compound from 1: 5 to 2: 1, preferably from 1: 3.
Exists 1: 1. Typically, aluminosilicate is
It is present in an amount of 3% to 15% of the antifoam of the present invention.

Optional Ingredients The foam control agent of the present invention may advantageously include glycerol in addition to the essential ingredients. Glycerol can be present in a weight ratio to the silicone antifoam of 1: 2 to 3: 1, and in an amount of 2-20%, preferably 8-15% of the antifoam of the present invention. Other optional ingredients include waxes and anti-caking agents.

Preferred waxes are of mineral origin, especially those derived from petroleum, such as microcrystalline and oxidized microcrystalline petroleum waxes and paraffin waxes. However, synthetic waxes or natural waxes such as montan wax, beeswax, candelilla wax and carbauba wax may also be used, and mixtures of any of these waxes may be used. Whatever the type of wax used, its melting point is preferably between 35 and 70 ° C. so that it can be easily liquefied.

Suitable anti-caking agents include alkoxylated nonionic surfactants, such as those described below.

Method for Producing the Antifoaming Agent of the Present Invention The present method basically comprises two steps, namely, (1) after aggregating a silicone antifoaming compound, a carrier substance and an organic coating substance, and (2) adding an aluminosilicate. Become.

1) Aggregation is performed using a standard aggregation unit (sugi-type or
(CB / KM type compounding machine) where the compound in both liquid and particulate form is fed to the agglomerator continuously (preferred option) or batchwise.

The compound in liquid form consists of a silicone antifoam compound and an organic coating that can be added in two separate streams or mixed before addition.

The compound in particulate form may be a carrier material (eg, starch)
Consists of

2) The addition of the aluminosilicate can be carried out in two different ways (options (a) and (b) below), the best feature of the method being that such an addition is
It is carried out at a temperature of 70 ° C., preferably in the range of 50 ° C. to 55 ° C.

Adding the zeolite at temperatures outside this range will not prepare free flowing granules.

Option 1: The product leaving the agglomerator at a temperature in the range of 45 ° C to 55 ° C is fed to a Regige KM tip (low energy high intensity) mixer where the aluminosilicate is added in the appropriate amount. The residence time in this mixer can be as short as 30 seconds, but can be as long as 3-4 minutes. The product is then fed to a fluidized bed and cooled to 25-35 ° C.

Option 2: The product leaving the agglomerator at a temperature in the range of 45 ° C to 55 ° C is fed to a two-compartment fluidized bed having a heating section and a cooling section. The product is "heated"
The first part of the fluidized bed is kept at 45-55 ° C. and aluminosilicate is blown into this part in an appropriate amount. The product is then fed to the second part of the fluidized bed and cooled to 25-35C.

Detergent Composition In another aspect of the present invention, there is provided a powdered detergent composition comprising a surfactant and a foam control agent as described above. The amount of antifoam is 0.25-10% by weight of the total detergent composition,
Preferably it is 0.5 to 3% by weight.

Suitable surfactants have an anionic, cationic, nonionic or amphoteric type, or a mixture thereof.
Suitable anionic organic detergent surfactants include alkali metal soaps of higher fatty acids, alkylaryl sulfonates such as sodium dodecylbenzene sulfonate,
Long-chain (fatty) alcohol sulfates, olefin sulfates and sulfonates, sulfated monoglycerides,
Includes sulfated ethers, sulfosuccinates, alkanesulfonates, phosphate esters, alkylisothionates, sucrose esters and fluorosurfactants. Suitable cationic organic detergent surfactants include alkylamine salts, quaternary ammonium salts, sulfonium salts and phosphonium salts. Suitable nonionic organic surfactants, condensation products of ethylene oxide with long chain (fatty) alcohol or fatty acid, for example, C _{14 to 15} alcohols engaged 7 mol ethylene oxide and condensation [Dobanol (Dobanol ^R) 45-7] , Condensates of ethylene oxide with amines or amides, ethylene oxide and propylene oxide, condensates of fatty acid alkylolamide and fatty amine oxide. Suitable amphoteric organic detergent surfactants include imidazoline compounds, alkyl amino acid salts and betaines.

The detergent composition of the present invention preferably also contains a builder, preferably of a non-phosphate type. Therefore,
The builder of the present invention preferably comprises an aluminosilicate ion exchanger (zeolite), and a water-soluble monomer or oligomer carboxylate chelating agent, such as, for example,
Citrate, succinate, oxydisuccinate,
And mixtures thereof.

Other suitable builder substances include alkali metal carbonates, bicarbonates and silicates, organic phosphonates, aminopolyalkylenephosphonates and aminopolycarboxylates, ethylenediaminetetraacetic acid and nitrilotriacetic acid. Other suitable water-soluble organic salts are homo- or copolymer polycarboxylic acids or salts thereof, wherein the polycarboxylic acid contains at least two carboxyl groups separated from each other by no more than two carbon atoms.
Such polymers are disclosed in GB 1,596,756. Examples of such salts are polyacrylates of MW 2000-5000, copolymers thereof with maleic anhydride (such copolymers have a molecular weight of 20,000-70,000, in particular about
40,000).

Other components that typically form part of the detergent composition in powder form include bleaching agents such as sodium perborate and sodium percarbonate, bleaching activators, anti-redeposition agents such as carboxymethyl cellulose, enzymes, enrichments. Whitening agents, fabric softening clays, perfumes, dyes, and pigments may be mentioned.

The above results show the effect of using zeolites to obtain properties such as density, compressibility, cake strength and the like.

Such properties are such that, contrary to the control agglomerates, the agglomerates of Example I are free-flowing and not sticky, and thus are perfectly suitable for dry incorporation into detergent compositions in powder form. Reflect the fact that.

The above results also indicate that the agglomerates of Example II are free flowing and not sticky, and thus are perfectly suitable for dry incorporation into detergent compositions in powder form.

A typical detergent composition in powder form incorporating the present defoamer in granular form has the following formula:

Abbreviations for the individual components have the following meanings.

LAS: sodium salt of linear dodecyl benzene sulfonate TAS: sodium salt of tallow alcohol sulfate FA45E7: fatty alcohol ethoxylated with ethylene oxide to about 7 mole (C ₁₄ ~C ₁₅₎ Clay: smectite clay Zeolite 4A: Average particle size 1 Sodium salt of zeolite 4A having 1010 μm AA / MA copolymer: copolymer of acrylic acid and maleic acid CMC: carboxymethylcellulose phosphonate: sodium salt of ethylenediaminetetramethylenephosphonic acid EDTA: sodium salt of ethylenediaminetetraacetic acid PB1: NaBO ₂ · H ₂ O ₂ (sodium perborate monohydrate) PB4: NaBO ₂ · H ₂ O ₂ · 3H ₂ O (sodium perborate tetrahydrate) TAED: tetraacetylethylenediamine

Continuation of the front page (72) Inventor de Cuperre, Marcel Joseph Jean Kessello, Belgium, Opés, de Briers, 14 (56) References JP-A-62-27496 (JP, A) JP-A-62 -27497 (JP, A) JP-A-4-311800 (JP, A) JP-A-61-271007 (JP, A) US Patent 4,513,871 (US, A) (58) Fields investigated (Int. Cl. ⁷ , (DB name) C11D 3/37 C11D 3/12 C11D 3/22

Claims (13)

(57) [Claims] 1. A stable free-flowing particulate foaming agent in granular form for incorporation into a powdered detergent composition comprising a silicone antifoaming compound, a carrier material and an organic coating material, wherein the foaming agent is further comprised of: A stable free-flowing foam control agent in granular form, comprising a crystalline or amorphous aluminosilicate, wherein the weight ratio of said aluminosilicate to the silicone defoaming compound is from 1: 5 to 2: 1. 2. A foam control agent according to claim 1, wherein the weight ratio of the aluminosilicate to the silicone antifoam compound is from 1: 3 to 1: 1. 3. The antifoaming agent according to claim 1, wherein the silicone antifoaming compound comprises a polydiorganosiloxane and solid silica. 4. The foam control agent according to claim 1, wherein the carrier substance is starch. 5. The organic coating agent is selected from water-soluble or water-dispersible substantially non-surfactant detergent-impermeable substances, water-insoluble fatty acids, and / or fatty alcohols and / or fatty acid esters, and mixtures thereof. The
The foam control agent according to any one of claims 1 to 4. 6. A water-soluble / dispersible organic coating agent comprising 25
6. A foam control agent according to claim 5, which is selected from highly ethoxylated fatty alcohols condensed with a mole to 80 mole ratio of ethylene oxide. 7. The water-insoluble fatty acid and / or fatty alcohol has a carbon chain length of 12 to 20 carbon atoms and a melting point of 45 ° C.
The foam control agent according to claim 5, which has a temperature of ~ 80 ° C. 8. The organic coating agent according to claim 6, wherein the organic coating agent is selected from stearic acid, stearyl alcohol, tallow fatty acid, tallow fatty alcohol, tallow alcohol condensed with 80 mole ratio of ethylene oxide, and a mixture thereof. Antifoaming agent. 9. Silicone antifoam 5-20% by weight, carrier material
40% to 80% by weight, organic coating substance 5 to 30% by weight,
The foam control agent according to any one of claims 1 to 8, comprising 3% to 15% by weight of zeolite. 10. The antifoaming agent according to claim 1, further comprising 2 to 20% by weight of glycerol. 11. A method according to claim 1, wherein the silicone antifoam compound, the carrier material and the organic coating material are coagulated together, and then the aluminosilicate is added to the agglomerate at a temperature in the range from 40 to 70 ° C. 11. The method for producing a foam control agent according to any one of 10 above. 12. The method of claim 11, wherein said temperature is in the range of 45 ° C. to 55 ° C. 13. A detergent composition in the form of a powder, comprising a surfactant and the antifoaming agent according to claim 1. Description: